Synthesis and characterization of Ru alkylidene complexes

ABSTRACT

This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, articles of manufacture comprising such compounds, and the use of such compounds in the metathesis of olefins and olefin compounds. The invention has utility in the fields of catalysts, organic synthesis, polymer chemistry, and industrial and fine chemicals industry.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/410,003, filed Oct. 19, 2016, and the benefit of U.S.Provisional Patent Application No. 62/509,269, filed May 22, 2017, thecontents of which are incorporated herein by reference.

TECHNICAL FIELD

This invention relates generally to olefin metathesis catalysts, to thepreparation of such compounds, compositions comprising such compounds,methods of using such compounds, and the use of such compounds in themetathesis of olefins and in the synthesis of related olefin metathesiscatalysts. The invention has utility in the fields of catalysis, organicsynthesis, polymer chemistry, and in industrial applications such as oiland gas, fine chemicals and pharmaceuticals.

BACKGROUND

Since its discovery in the 1950s, olefin metathesis has emerged as avaluable synthetic method for the formation of carbon-carbon doublebonds. Recent advances in applications to organic syntheses and polymersyntheses mostly rely on developments of well-defined olefin metathesiscatalysts.

The technology of ruthenium metathesis catalysts has enabled thedevelopment of several research platforms including: ring openingmetathesis polymerization (ROMP), ring opening cross metathesis (ROCM),cross metathesis (CM), ring closing metathesis (RCM).

The incorporation of N-Heterocyclic Carbene (NHC) ligands has played anessential role in the development of ruthenium metathesis catalysts.Metathesis catalysts, based on ruthenium, are known and have beenstudied.

However, there is an ongoing need for olefin metathesis catalysts,particularly ruthenium metathesis catalysts with improvedcharacteristics which will further enable their use in a wider array ofapplications and olefin metathesis reactions, and for methods to preparethem.

SUMMARY OF THE INVENTION

To meet this need the inventors have discovered various olefinmetathesis catalysts as described herein.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (I):

wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium;typically M is ruthenium;

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F;

L¹ is a ligand represented by the structure of Formula (II), or is anNHC ligand represented by the structure of Formula (III):

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, or substituted saturatedN-heterocycle;

Y is CR⁴ or N;

R⁴ is hydrogen, unsubstituted (C₁-C₁₂ alkyl), or substituted (C₁-C₁₂alkyl);

R⁵ and R⁶ are independently hydrogen, unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₅-C₂₄ aryl);

Q is a two-atom linkage represented by structures—[CR⁷R⁸]_(s)—[CR⁹R¹⁰]_(t)— or —[CR¹¹═CR¹²]—;

R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, unsubstituted (C₁-C₂₄alkyl), substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₅-C₂₄ aryl); or any two of R⁷, R⁸, R⁹ and R¹⁰ areoptionally linked together to form a substituted or unsubstituted,saturated or unsaturated ring structure;

R¹¹ and R¹² are independently hydrogen, unsubstituted (C₁-C₂₄ alkyl),substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), or substituted(C₅-C₂₄ aryl); or R¹¹ and R¹² are optionally linked together to form asubstituted or unsubstituted, saturated or unsaturated ring structure;and

“s” and “t” are independently 1 or 2; typically “s” and “t” areindependently 1.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (IV):

wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium;typically M is ruthenium;

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F;

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; and

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (V):

wherein:

M is a Group 8 transition metal; generally M is ruthenium or osmium;typically M is ruthenium;

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F;

X³ is phenyl

or 2-methyl-1-propenyl (—CH═C(CH₃)₂ or

L¹ is a ligand represented by the structure of Formula (II), or is anNHC ligand represented by the structure of Formula (III):

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, unsubstituted unsaturated N-heterocycle, substitutedunsaturated N-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂,—NH(C₅-C₂₄ aryl), —N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl),—N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂, or —O—(C₁-C₁₂ alkyl);

R² is unsubstituted (C₅-C₂₄ cycloalkyl), substituted (C₅-C₂₄cycloalkyl), unsubstituted saturated N-heterocycle, substitutedsaturated N-heterocycle, unsubstituted (C₅-C₂₄ aryl), substituted(C₅-C₂₄ aryl), —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ cycloalkyl), substituted (C₅-C₂₄cycloalkyl), unsubstituted saturated N-heterocycle, substitutedsaturated N-heterocycle, unsubstituted (C₅-C₂₄ aryl), or substituted(C₅-C₂₄ aryl);

Y is CR⁴ or N;

R⁴ is hydrogen, unsubstituted (C₁-C₁₂ alkyl), or substituted (C₁-C₁₂alkyl);

R⁵ and R⁶ are independently hydrogen, unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₅-C₂₄ aryl);

Q is a two-atom linkage represented by structures—[CR⁷R⁸]_(s)—[CR⁹R¹⁰]_(t)— or —[CR¹¹═CR¹²]—;

R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, unsubstituted (C₁-C₂₄alkyl), substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₅-C₂₄ aryl); or any two of R⁷, R⁸, R⁹ and R¹⁰ areoptionally linked together to form a substituted or unsubstituted,saturated or unsaturated ring structure;

R¹¹ and R¹² are independently hydrogen, unsubstituted (C₁-C₂₄ alkyl),substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), or substituted(C₅-C₂₄ aryl); or R¹¹ and R¹² are optionally linked together to form asubstituted or unsubstituted, saturated or unsaturated ring structure;and

“s” and “t” are independently 1 or 2; typically “s” and “t” areindependently 1.

In one embodiment, the invention provides a method of synthesizing theolefin metathesis catalysts of the invention.

In one embodiment, the invention provides a method of using the olefinmetathesis catalysts of the invention in metathesis reactions. Theolefin metathesis catalysts of the invention are of particular benefitfor use in metathesis reactions, such as ring opening metathesispolymerization reactions, ring-opening cross metathesis reactions, crossmetathesis reactions, ring-closing metathesis reactions, self-metathesisreactions, as well as combinations of such metathesis reactions.

The olefin metathesis catalysts of the invention are also keyintermediates in the synthesis of a variety of ruthenium olefinmetathesis catalysts.

These and other aspects of the present invention will be apparent to theskilled artisan in light of the following detailed description andexamples. Furthermore, it is to be understood that none of theembodiments or examples of the invention described herein are to beinterpreted as being limiting.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C940.

FIG. 2. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C958.

FIG. 3. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C852.

FIG. 4. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C803.

FIG. 5. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C850.

FIG. 6. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C825.

FIG. 7. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C832.

FIG. 8. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C865.

FIG. 9. Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C829.

FIG. 10. Vinyl ether quenching experiments for catalysts: C849, C865,C825, C850, C852, and C832.

FIG. 11. Vinyl ether quenching experiments for catalysts: C831, C840,C849, and C858.

FIG. 12. Vinyl ether quenching experiments for catalysts: C848, C852,C855, C858.

DETAILED DESCRIPTION

Unless otherwise indicated, the invention is not limited to specificreactants, substituents, catalysts, reaction conditions, or the like, assuch can vary. It is also to be understood that the terminology usedherein is for the purpose of describing particular embodiments only andis not to be interpreted as being limiting.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “an olefin” includesa single olefin as well as a combination or mixture of two or moreolefins, reference to “a substituent” encompasses a single substituentas well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “forexample,” “for instance,” “such as,” or “including” are meant tointroduce examples that further clarify more general subject matter.Unless otherwise specified, these examples are provided only as an aidfor understanding the invention, and are not meant to be limiting in anyfashion.

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group typically although not necessarilycontaining generally 1 to 30 carbon atoms, typically 1 to 12 carbonatoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups suchas cyclopentyl, cyclohexyl and the like. The term “lower alkyl” intendsan alkyl group of 1 to 6 carbon atoms, and the specific term“cycloalkyl” intends a cyclic alkyl group, typically having 4 to 8,preferably 5 to 7, carbon atoms. The term “substituted alkyl” refers toalkyl substituted with one or more substituent groups, and the terms“heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in whichat least one carbon atom is replaced with a heteroatom. If not otherwiseindicated, the terms “alkyl” and “lower alkyl” include linear, branched,cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyland lower alkyl, respectively.

The term “alkylene” as used herein refers to a divalent linear,branched, or cyclic alkyl group, where “alkyl” is as defined above.

The term “alkenyl” as used herein refers to a linear, branched, orcyclic hydrocarbon group of 2 to 30 carbon atoms containing at least onedouble bond, such as ethenyl, n-propenyl, iso-propenyl, n-butenyl,iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl,tetracosenyl, and the like. Typically alkenyl groups herein contain 2 to12 carbon atoms. The term “lower alkenyl” intends an alkenyl group of 2to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclicalkenyl group, typically having 5 to 8 carbon atoms. The term“substituted alkenyl” refers to alkenyl substituted with one or moresubstituent groups, and the terms “heteroatom-containing alkenyl” and“heteroalkenyl” refer to alkenyl in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkenyl” and “lower alkenyl” include linear, branched, cyclic,unsubstituted, substituted, and/or heteroatom-containing alkenyl andlower alkenyl, respectively. The term “alkenyl” is used interchangeablywith the term “olefin” herein.

The term “alkenylene” as used herein refers to a divalent linear,branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

The term “alkynyl” as used herein refers to a linear or branchedhydrocarbon group of 2 to 30 carbon atoms containing at least one triplebond, such as ethynyl, n-propynyl, and the like. Typical alkynyl groupsdescribed herein contain 2 to 12 carbon atoms. The term “lower alkynyl”intends an alkynyl group of 2 to 6 carbon atoms. The term “substitutedalkynyl” refers to alkynyl substituted with one or more substituentgroups, and the terms “heteroatom-containing alkynyl” and“heteroalkynyl” refer to alkynyl in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkynyl” and “lower alkynyl” include linear, branched, unsubstituted,substituted, and/or heteroatom-containing alkynyl and lower alkynyl,respectively.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group can berepresented as —O-alkyl where alkyl is as defined above. A “loweralkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer toan alkenyl and lower alkenyl group bound through a single, terminalether linkage, and “alkynyloxy” and “lower alkynyloxy” respectivelyrefer to an alkynyl and lower alkynyl group bound through a single,terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, directly linked, or indirectlylinked (such that the different aromatic rings are bound to a commongroup such as a methylene or ethylene moiety). Generally aryl groupscontain 5 to 30 carbon atoms, and typically aryl groups contain 5 to 14carbon atoms. Exemplary aryl groups contain one aromatic ring or twofused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl,diphenylether, diphenylamine, benzophenone, and the like. “Substitutedaryl” refers to an aryl moiety substituted with one or more substituentgroups. The terms “heteroatom-containing aryl” and “heteroaryl” refer toaryl substituents in which at least one carbon atom is replaced with aheteroatom, as will be described in further detail infra.

The term “aryloxy” as used herein refers to an aryl group bound througha single, terminal ether linkage, wherein “aryl” is as defined above. An“aryloxy” group can be represented as —O-aryl where aryl is as definedabove. Preferred aryloxy groups contain 5 to 24 carbon atoms, andparticularly preferred aryloxy groups contain 5 to 14 carbon atoms.Examples of aryloxy groups include, without limitation, phenoxy,o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy,m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy,3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent,and the term “aralkyl” refers to an alkyl group with an arylsubstituent, wherein “aryl” and “alkyl” are as defined above. Generallyalkaryl and aralkyl groups contain 6 to 30 carbon atoms, and typicallyalkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl groupsinclude, for example, p-methylphenyl, 2,4-dimethylphenyl,p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl,3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl groupsinclude, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl,4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl,4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. Theterms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula—OR wherein R is alkaryl or aralkyl, respectively, as defined herein.

The term “acyl” refers to substituents having the formula —(CO)-alkyl,—(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers tosubstituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or—O(CO)-aralkyl, wherein “alkyl,” “aryl,” and “aralkyl” are as definedabove.

The terms “cyclic” and “ring” refer to moieties which are saturated orhave unsaturations and are non-aromatic or are aromatic and that areoptionally substituted and/or heteroatom containing, and that can bemonocyclic, bicyclic, or polycyclic.

The term “saturated N-heterocycle” as used herein refers to aheteroatom-containing cyclic group, which is saturated and is attachedto the rest of the molecule by a nitrogen (N) atom. The saturatedN-heterocycle moiety contains rings wherein one or more carbon(s) hasbeen replaced by a heteroatom, such as: N, S or O. Unsubstituted“saturated N-heterocycle” groups include pyrrolidino, morpholino,piperazino, piperidino, thiomorpholino, etc. Substituted “saturatedN-heterocycle” groups include 1-methyl-piperazino, N-acetyl-piperazino,N-ethylcarboxylate-piperazino, etc.

The terms “halo,” “halogen,” and “halide” are used in the conventionalsense to refer to a chloro, bromo, fluoro, or iodo substituent.

The term “hydrocarbyl” refers to univalent hydrocarbyl radicalscontaining 1 to 30 carbon atoms, typically containing 1 to 24 carbonatoms, specifically containing 1 to 12 carbon atoms, including linear,branched, cyclic, saturated, and unsaturated species, such as alkylgroups, alkenyl groups, aryl groups, and the like. The term “lowerhydrocarbyl” intends a hydrocarbyl group of 1 to 6 carbon atoms,typically 1 to 4 carbon atoms, and the term “hydrocarbylene” intends adivalent hydrocarbyl moiety containing 1 to 30 carbon atoms, typically 1to 24 carbon atoms, specifically 1 to 12 carbon atoms, including linear,branched, cyclic, saturated and unsaturated species. The term “lowerhydrocarbylene” intends a hydrocarbylene group of 1 to 6 carbon atoms.“Substituted hydrocarbyl” refers to hydrocarbyl substituted with one ormore substituent groups, and the terms “heteroatom-containinghydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which atleast one carbon atom is replaced with a heteroatom. Similarly,“substituted hydrocarbylene” refers to hydrocarbylene substituted withone or more substituent groups, and the terms “heteroatom-containinghydrocarbylene” and “heterohydrocarbylene” refer to hydrocarbylene inwhich at least one carbon atom is replaced with a heteroatom. Unlessotherwise indicated, the term “hydrocarbyl” and “hydrocarbylene” are tobe interpreted as including substituted and/or heteroatom-containinghydrocarbyl and hydrocarbylene moieties, respectively.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbylmolecular fragment in which one or more carbon atoms is replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus orsilicon, typically nitrogen, oxygen or sulfur. Similarly, the term“heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the terms “heteroaryl” and“heteroaromatic” respectively refer to “aryl” and “aromatic”substituents that are heteroatom-containing, and the like. It should benoted that a “heterocyclic” group or compound is optionally aromatic,and further that “heterocycles” can be monocyclic, bicyclic, orpolycyclic as described above with respect to the term “aryl.” Examplesof heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substitutedalkyl, N-alkylated amino alkyl, and the like. Examples of heteroarylsubstituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl,indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.

By “Grubbs-Hoveyda ligands,” is meant benzylidene ligands having achelating alkyloxy group attached to the benzene ring at the orthoposition.

Examples of —NH(C₁-C₂₄ alkyl) groups include —NHMe (e.g., methylamino),—NHEt (e.g., ethylamine), —NH(i-Pr) (e.g., iso-propylamino), etc.

Examples of —N(C₁-C₂₄ alkyl)₂ groups include —N(Me)₂ (e.g.,dimethylamino), —N(Et)₂ (e.g., diethylamino), —N(i-Pr)₂ (e.g.,di-iso-propylamino), etc.

Examples of —NH(C₅-C₂₄ aryl) groups include —NH(C₆Hs) (e.g.,phenylamino), etc.

Examples of —N(C₅-C₂₄ aryl)₂ groups include —N(C₆H₅)₂ (e.g.,diphenylamino), etc.

Examples of —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) groups include —NMe(C₆H₅)(e.g., phenylmethylamino), etc.

Examples of —N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂ groups include—N[(CH₂)(C₆H₅)]₂ (e.g., di-benzyl-amino), etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,”“substituted aryl,” and the like, as alluded to in some of theaforementioned definitions, is meant that in the hydrocarbyl, alkyl,aryl, or other moiety, at least one hydrogen atom bound to a carbon (orother) atom is replaced with one or more non-hydrogen substituents.Examples of such substituents include, without limitation: functionalgroups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl,C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO—), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl,thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CS)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl(—(CS)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CS)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted thiocarbamoyl(—(CS)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄aryl)-substituted thiocarbamoyl, carbamido (—NH—(CO)—NH₂), cyano(—C≡N),cyanato (—O—C≡N), thiocyanato (—S—C≡N), formyl (—(CO)—H), thioformyl(—(CS)—H), amino (—NH₂), mono-(C₁-C₂₄ alkyl)-substituted amino,di-(C₁-C₂₄ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substitutedamino, di-(C₅-C₂₄ aryl)-substituted amino, (C₁-C₂₄ alkyl)(C₅-C₂₄aryl)-substituted amino, C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (—CR═NH where R=hydrogen, C₁-C₂₄ alkyl,C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), C₂-C₂₀ alkylimino(—CR═N(alkyl), where R=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), whereR=hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl,etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O—), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl —SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl —SO₂—N(alkyl)₂, C₅-C₂₄ arylsulfonyl(—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where Ris alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O—)₂), phosphinato (—P(O)(O—)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂alkenyl, more preferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferablyC₂-C₁₂ alkynyl, more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl (preferablyC₅-C₁₄ aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄aralkyl (preferably C₆-C₁₆ aralkyl).

By “functionalized” as in “functionalized hydrocarbyl,” “functionalizedalkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and thelike, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, orother moiety, at least one hydrogen atom bound to a carbon (or other)atom is replaced with one or more functional groups such as thosedescribed hereinabove. The term “functional group” is meant to includeany functional species that is suitable for the uses described herein.In particular, as used herein, a functional group would necessarilypossess the ability to react with or bond to corresponding functionalgroups on a substrate surface.

In addition, the aforementioned functional groups can, if a particulargroup permits, be further substituted with one or more additionalfunctional groups or with one or more hydrocarbyl moieties such as thosespecifically enumerated above. Analogously, the above-mentionedhydrocarbyl moieties can be further substituted with one or morefunctional groups or additional hydrocarbyl moieties such as thosespecifically enumerated.

“Optional” or “optionally” means that the subsequently describedcircumstance can or cannot occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent can or cannot be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

Olefin Metathesis Catalysts

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (VI):

wherein:

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F;

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂; generally R¹ is unsubstituted saturated N-heterocycle,substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₆ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃alkylene)(C₆ aryl)]₂; and

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₆ aryl) or unsubstitutedsaturated N-heterocycle.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (VI), wherein X¹ isCl; X² is Cl; R¹ is morpholino, thiomorpholino, 1-methyl-piperazino,piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; R² is phenyl, morpholino, thiomorpholino,1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; and R³ is phenyl or morpholino.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (VII):

wherein:

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F;

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R¹ is unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂,—N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₆ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃alkylene)(C₆ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₆ aryl) or substitutedsaturated N-heterocycle;

Y is CR⁴ or N; generally Y is N;

R⁴ is hydrogen, unsubstituted (C₁-C₁₂ alkyl), or substituted (C₁-C₁₂alkyl);

R⁵ and R⁶ are independently hydrogen, unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₅-C₂₄ aryl); generally R⁵ and R⁶ are independentlysubstituted (C₅-C₂₄ aryl);

Q is a two-atom linkage represented by structures—[CR⁷R⁸]_(s)—[CR⁹R¹⁰]_(t)— or —[CR¹¹═CR¹²]—;

R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, unsubstituted (C₁-C₂₄alkyl), substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₁-C₂₄ aryl); or any two of R⁷, R⁸, R⁹ and R¹⁰ areoptionally linked together to form a substituted or unsubstituted,saturated or unsaturated ring structure; generally R⁷, R⁸, R⁹ and R¹⁰are independently hydrogen, unsubstituted (C₁-C₁₂ alkyl), substituted(C₁-C₁₂ alkyl), unsubstituted (C₅-C₁₄ aryl) or substituted (C₅-C₁₄aryl);

R¹¹ and R¹² are independently hydrogen, unsubstituted (C₁-C₂₄ alkyl),substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), or substituted(C₅-C₂₄ aryl); or R¹¹ and R¹² are optionally linked together to form asubstituted or unsubstituted, saturated or unsaturated ring structure;and

“s” and “t” are independently 1 or 2; generally “s” and “t” areindependently 1.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (VIII):

wherein:

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F;

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R¹ is unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂,—N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₆ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃alkylene)(C₆ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₆ aryl) or unsubstitutedsaturated N-heterocycle; and

R⁵ and R⁶ are independently hydrogen, unsubstituted C₅-C₂₄ aryl, orsubstituted C₅-C₂₄ aryl; generally R⁵ and R⁶ are independentlysubstituted C₅-C₂₄ aryl with one to three unsubstituted (C₁-C₆ alkyl)groups or substituted (C₁-C₆ alkyl) groups.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (VIII), wherein X¹ isCl; X² is Cl; R¹ is morpholino, thiomorpholino, 1-methyl-piperazino,piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; R² is phenyl, morpholino, thiomorpholino,1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; R³ is phenyl or morpholino; and R⁵ and R⁶ areindependently 2,4,6-trimethyl-phenyl (e.g., mesityl or Mes),2,6-di-iso-propylphenyl (e.g., DIPP or DiPP), 2-iso-propylphenyl (e.g.,IPP or Ipp), or 2-methyl-6-iso-propylphenyl (e.g., MIPP or Mipp orMiPP).

Some of the olefin metathesis catalysts represented by the structure ofFormula (VIII) were obtained as solvates.

In one embodiment, the invention provides an olefin metathesis catalyst,represented by the structure of Formula (IVa):

wherein:

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F;

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R¹ is unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂,—N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₆ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃alkylene)(C₆ aryl)]₂; and

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R³ is unsubstituted (C₆ aryl) orunsubstituted saturated N-heterocycle.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (IVa), wherein X¹ isCl; X² is Cl; R¹ is morpholino, thiomorpholino, 1-methyl-piperazino,piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; R² is phenyl, morpholino, thiomorpholino,1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; and R³ is phenyl or morpholino.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (IX):

wherein:

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F;

X³ is phenyl or 2-methyl-1-propenyl;

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, unsubstituted unsaturated N-heterocycle, substitutedunsaturated N-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂,—NH(C₅-C₂₄ aryl), —N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl),—N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂, or —O—(C₁-C₁₂ alkyl); generally R¹is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —O—(C₁-C₁₂ alkyl), or unsubstituted unsaturatedN-heterocycle;

R² is unsubstituted (C₅-C₂₄ cycloalkyl), substituted (C₅-C₂₄cycloalkyl), unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₅-C₂₄cycloalkyl), unsubstituted (C₆ aryl), unsubstituted saturatedN-heterocycle; and

R³ is unsubstituted (C₅-C₂₄ cycloalkyl), substituted (C₅-C₂₄cycloalkyl), unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₅-C₂₄ cycloalkyl),unsubstituted (C₆ aryl) or unsubstituted saturated N-heterocycle.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (IX), wherein X¹ isCl; X² is Cl; X³ is phenyl; R¹ is morpholino, iso-propoxyl, pyrrolo; R²is cyclohexyl, phenyl or morpholino; and R³ is cyclohexyl, phenyl ormorpholino.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (IX), wherein X¹ isCl; X² is Cl; X³ is 2-methyl-1-propenyl; R¹ is morpholino, iso-propoxyl,pyrrolo; R² is cyclohexyl, phenyl or morpholino; and R³ is cyclohexyl,phenyl or morpholino.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (X):

wherein:

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F; X³ is phenyl or2-methyl-1-propenyl;

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, unsubstituted unsaturated N-heterocycle, substitutedunsaturated N-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂,—NH(C₅-C₂₄ aryl), —N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl),—N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂, or —O—(C₁-C₁₂ alkyl); generally R¹is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —O—(C₁-C₁₂ alkyl), —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ cycloalkyl), substituted (C₅-C₂₄cycloalkyl), unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₅-C₂₄cycloalkyl), unsubstituted (C₆ aryl), unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂,—N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ cycloalkyl), substituted (C₅-C₂₄cycloalkyl), unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₅-C₂₄ cycloalkyl),unsubstituted (C₆ aryl) or unsubstituted saturated N-heterocycle;

Y is CR⁴ or N; generally Y is N;

R⁴ is hydrogen, unsubstituted (C₁-C₁₂ alkyl), or substituted (C₁-C₁₂alkyl);

R⁵ and R⁶ are independently hydrogen, unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₅-C₂₄ aryl); generally R⁵ and R⁶ are independentlysubstituted (C₅-C₂₄ aryl);

Q is a two-atom linkage represented by structures—[CR⁷R⁸]_(s)—[CR⁹R¹⁰]_(t)— or —[CR¹¹═CR¹²]—;

R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, unsubstituted (C₁-C₂₄alkyl), substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₁-C₂₄ aryl); or any two of R⁷, R⁸, R⁹ and R¹⁰ areoptionally linked together to form a substituted or unsubstituted,saturated or unsaturated ring structure; generally R⁷, R⁸, R⁹ and R¹⁰are independently hydrogen, unsubstituted (C₁-C₁₂ alkyl), substituted(C₁-C₁₂ alkyl), unsubstituted (C₅-C₁₄ aryl) or substituted (C₅-C₁₄aryl);

R¹¹ and R¹² are independently hydrogen, unsubstituted (C₁-C₂₄ alkyl),substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), or substituted(C₅-C₂₄ aryl); or R¹¹ and R¹² are optionally linked together to form asubstituted or unsubstituted, saturated or unsaturated ring structure;and

“s” and “t” are independently 1 or 2; generally “s” and “t” areindependently 1.

In one embodiment, the invention provides olefin metathesis catalysts,represented by the structure of Formula (XI),

wherein:

X¹ and X² are independently anionic ligands; generally X¹ and X² areindependently halogen, trifluoroacetate, per-fluorophenols or nitrate;typically X¹ and X² are independently Cl, Br, I or F; X³ is phenyl or2-methyl-1-propenyl;

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, unsubstituted unsaturated N-heterocycle, substitutedunsaturated N-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂,—NH(C₅-C₂₄ aryl), —N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl),—N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂, or —O—(C₁-C₁₂ alkyl); generally R¹is unsubstituted saturated N-heterocycle, unsubstituted unsaturatedN-heterocycle, —O—(C₁-C₁₂ alkyl);

R² is unsubstituted (C₅-C₂₄ cycloalkyl), substituted (C₅-C₂₄cycloalkyl), unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₅-C₂₄cycloalkyl), unsubstituted (C₆ aryl), unsubstituted saturatedN-heterocycle;

R³ is unsubstituted (C₅-C₂₄ cycloalkyl), substituted (C₅-C₂₄cycloalkyl), unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₅-C₂₄ cycloalkyl),unsubstituted (C₆ aryl) or unsubstituted saturated N-heterocycle; and

R⁵ and R⁶ are independently unsubstituted (C₅-C₂₄ aryl), or substituted(C₅-C₂₄ aryl); generally R⁵ and R⁶ are independently substituted (C₅-C₂₄aryl) with one to three unsubstituted (C₁-C₆ alkyl) groups orsubstituted (C₁-C₆ alkyl) groups.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (XI), wherein X¹ isCl; X² is Cl; X³ is phenyl; R¹ is morpholino, isopropoxy, pyrrolo orpiperidino; R² is cyclohexyl, morpholino, piperidino or phenyl; R³ isphenyl, morpholino, piperidino or cyclohexyl; and R⁵ and R⁶ areindependently 2,4,6-trimethyl-phenyl, 2,6-di-iso-propylphenyl,2-iso-propylphenyl, or 2-methyl-6-iso-propylphenyl.

In another embodiment, the invention provides an olefin metathesiscatalyst, represented by the structure of Formula (XI), wherein X¹ isCl; X² is Cl; X³ is 2-methyl-1-propenyl; R¹ is morpholino, isopropoxy,pyrrolo or piperidino; R² is cyclohexyl, morpholino, piperidino orphenyl; R³ is phenyl, morpholino, piperidino or cyclohexyl; and R⁵ andR⁶ are independently 2,4,6-trimethyl-phenyl, 2,6-di-iso-propylphenyl,2-iso-propylphenyl, or 2-methyl-6-iso-propylphenyl.

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (VI) are found in Table (1):

TABLE (1) Non-limiting examples of olefin metathesis catalystsrepresented by Formula (VI) Catalyst R¹ R² R³ X¹ X² 1

Cl Cl 2

Cl Cl 3

Cl Cl 4

Cl Cl 5

Cl Cl 6

Cl Cl 7

Cl Cl 8

Cl Cl 9

Cl Cl 10

Cl Cl 11

Cl Cl 12

Cl Cl 13

Cl Cl 14

Cl Cl 15

Cl Cl 16

Cl Cl 17

Cl Cl 18

Cl Cl 19

Cl Cl 20

Cl Cl 21

Cl Cl

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (VIII) are found in Table (2):

TABLE 2 Non-limiting examples of olefin metathesis catalysts representedby Formula (VIII) Catalyst R¹ R² R³ X¹ X² R⁵ R⁶ 22

Cl Cl Mes Mes 23

Cl Cl Mes Mes 24

Cl Cl Mes Mes 25

Cl Cl Mes Mes 26

Cl Cl Mes Mes 27

Cl Cl Mes Mes 28

Cl Cl Mes Mes 29

Cl Cl Mes Mes 30

Cl Cl Mes Mes 31

Cl Cl Mes Mes 32

Cl Cl Mes Mes 33

Cl Cl Mes Mes 34

Cl Cl Mes Mes 35

Cl Cl Mes Mes 36

Cl Cl Mes Mes 37

Cl Cl Mes Mes 38

Cl Cl Mes Mes 39

Cl Cl Mes Mes 40

Cl Cl Mes Mes 41

Cl Cl Mes Mes 42

Cl Cl Mes Mes 43

Cl Cl DIPP DIPP 44

Cl Cl DIPP DIPP 45

Cl Cl DIPP DIPP 46

Cl Cl DIPP DIPP 47

Cl Cl DIPP DIPP 48

Cl Cl DIPP DIPP 49

Cl Cl DIPP DIPP 50

Cl Cl DIPP DIPP 51

Cl Cl DIPP DIPP 52

Cl Cl DIPP DIPP 53

Cl Cl DIPP DIPP 54

Cl Cl DIPP DIPP 55

Cl Cl DIPP DIPP 56

Cl Cl DIPP DIPP 57

Cl Cl DIPP DIPP 58

Cl Cl DIPP DIPP 59

Cl Cl DIPP DIPP 60

Cl Cl DIPP DIPP 61

Cl Cl DIPP DIPP 62

Cl Cl DIPP DIPP 63

Cl Cl DIPP DIPP 64

Cl Cl MIPP MIPP 65

Cl Cl MIPP MIPP 66

Cl Cl MIPP MIPP 67

Cl Cl MIPP MIPP 68

Cl Cl MIPP MIPP 69

Cl Cl MIPP MIPP 70

Cl Cl MIPP MIPP 71

Cl Cl MIPP MIPP 72

Cl Cl MIPP MIPP 73

Cl Cl MIPP MIPP 74

Cl Cl MIPP MIPP 75

Cl Cl MIPP MIPP 76

Cl Cl MIPP MIPP 77

Cl Cl MIPP MIPP 78

Cl Cl MIPP MIPP 79

Cl Cl MIPP MIPP 80

Cl Cl MIPP MIPP 81

Cl Cl MIPP MIPP 82

Cl Cl MIPP MIPP 83

Cl Cl MIPP MIPP 84

Cl Cl MIPP MIPP wherein: Mes is

MIPP is

and DIPP is

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (IVa) are found in Table (3):

TABLE 3 Non-limiting examples of olefin metathesis catalysts representedby the structure of Formula (IVa) Catalyst R¹ R² R³ X¹ X² 85

Cl Cl 86

Cl Cl 87

Cl Cl 88

Cl Cl 89

Cl Cl 90

Cl Cl 91

Cl Cl 92

Cl Cl 93

Cl Cl 94

Cl Cl 95

Cl Cl 96

Cl Cl 97

Cl Cl 98

Cl Cl 99

Cl Cl 100

Cl Cl 101

Cl Cl 102

Cl Cl 103

Cl Cl 104

Cl Cl 105

Cl Cl

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (IX) are found in Table (4):

TABLE 4 Non-limiting examples of olefin metathesis catalysts representedby the structure of Formula (IX) Catalyst R¹ R² R³ X¹ X² X³ 106

Cl Cl

107

Cl Cl

108

Cl Cl

109

Cl Cl

110

Cl Cl

111

Cl Cl

112

Cl Cl

113

Cl Cl

114

Cl Cl

115

Cl Cl

116

Cl Cl

117

Cl Cl

118

Cl Cl

119

Cl Cl

Non-limiting examples of olefin metathesis catalysts represented by thestructure of Formula (IX) are found in Table (5):

TABLE 5 Non-limiting examples of olefin metathesis catalysts representedby the structure of Formula (XI) Catalyst R¹ R² R³ X¹ X² X³ R⁵ R⁶ 120

Cl Cl

Mes Mes 121

Cl Cl

Mes Mes 122

Cl Cl

Mes Mes 123

Cl Cl

Mes Mes 124

Cl Cl

Mes Mes 125

Cl Cl

Mes Mes 126

Cl Cl

Mes Mes 127

Cl Cl

Mes Mes 128

Cl Cl

Mes Mes 129

Cl Cl

Mes Mes 130

Cl Cl

Mes Mes 131

Cl Cl

Mes Mes 132

Cl Cl

Mes Mes 133

Cl Cl

Mes Mes 134

Cl Cl

Mes Mes 135

Cl Cl

Mes Mes 136

Cl Cl

Mes Mes 137

Cl Cl

Mes Mes 138

Cl Cl

Mes Mes 139

Cl Cl

Mes Mes 140

Cl Cl

DIPP DIPP 141

Cl Cl

DIPP DIPP 142

Cl Cl

DIPP DIPP 143

Cl Cl

DIPP DIPP 144

Cl Cl

DIPP DIPP 145

Cl Cl

DIPP DIPP 146

Cl Cl

DIPP DIPP 147

Cl Cl

DIPP DIPP 148

Cl Cl

DIPP DIPP 149

Cl Cl

DIPP DIPP 150

Cl Cl

DIPP DIPP 151

Cl Cl

DIPP DIPP 152

Cl Cl

DIPP DIPP 153

Cl Cl

DIPP DIPP 154

Cl Cl

DIPP DIPP 155

Cl Cl

DIPP DIPP 156

Cl Cl

DIPP DIPP 157

Cl Cl

DIPP DIPP 158

Cl Cl

DIPP DIPP 158

Cl Cl

DIPP DIPP 159

Cl Cl

MIPP MIPP 160

Cl Cl

MIPP MIPP 161

Cl Cl

MIPP MIPP 162

Cl Cl

MIPP MIPP 163

Cl Cl

MIPP MIPP 164

Cl Cl

MIPP MIPP 165

Cl Cl

MIPP MIPP 166

Cl Cl

MIPP MIPP 167

Cl Cl

MIPP MIPP 168

Cl Cl

MIPP MIPP 169

Cl Cl

MIPP MIPP 170

Cl Cl

MIPP MIPP 171

Cl Cl

MIPP MIPP 172

Cl Cl

MIPP MIPP 173

Cl Cl

MIPP MIPP 174

Cl Cl

MIPP MIPP 175

Cl Cl

MIPP MIPP 176

Cl Cl

MIPP MIPP 177

Cl Cl

MIPP MIPP 178

Cl Cl

MIPP MIPP

The present invention concerns also processes for preparing the olefinmetathesis catalysts described above. The olefin metathesis catalystsaccording to the invention can be prepared analogously to conventionalmethods as understood by the person skilled in the art of syntheticorganic chemistry.

Synthetic Scheme 1 illustrates how the olefin metathesis catalysts ofFormula (VI), Formula (VII), and Formula (VIII) can be synthesized.

Synthetic Scheme 2 illustrates how olefin metathesis catalysts ofFormula (IVa) can be synthesized.

Synthetic Scheme 3 illustrates how the olefin metathesis catalysts ofFormula (IX), Formula (X), and Formula (XI) can be synthesized.

In synthetic Schemes 1, 2, and 3, substituents X¹, X², X³, R¹, R², R³,Q, Y, R⁵, and R⁶ are as defined herein.

Generally, the reactions take place under degassed N₂ at roomtemperature or at high temperature in an inert solvent (toluene, THF,MeTHF, dioxane and the like). Once the reaction is completed, themixture is cooled to room temperature, the solvent is removed under highvacuum, and the residue is purified on a silica gel column and thenrecrystallized to afford the new olefin metathesis catalysts.

In another embodiment, the invention concerns methods of using theolefin metathesis catalysts of the invention, in the synthesis ofrelated olefin metathesis catalysts. The ruthenium olefin metathesiscatalysts of the invention are excellent precursors for various SecondGeneration Grubbs ruthenium olefin metathesis catalysts. The SecondGeneration Grubbs ruthenium olefin metathesis catalysts synthesizedduring these procedures are obtained in higher yield and with higherpurity, which presents an advantage compared to the existing syntheticprocedures.

The invention concerns also processes for synthesizing olefin metathesiscatalysts of Formula (A) starting with an olefin metathesis catalyst ofFormula (VIII).

In a typical procedure, as shown in Scheme 4, the PR¹R²R³ ligand of theolefin metathesis catalyst represented by Formula (VIII) can beexchanged with a PR^(d)R^(e)OR^(f) ligand at room temperature in aninert solvent, such as dichloromethane or toluene, wherein:

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R¹ is unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂,—N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₆ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃alkylene)(C₆ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₆ aryl) or unsubstitutedsaturated N-heterocycle;

R⁵ and R⁶ are independently hydrogen, unsubstituted C₅-C₂₄ aryl, orsubstituted C₅-C₂₄ aryl; generally R⁵ and R⁶ are independentlysubstituted C₅-C₂₄ aryl with one to three unsubstituted (C₁-C₆ alkyl)groups or substituted (C₁-C₆ alkyl) groups; typically, R⁵ and R⁶ areindependently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propylphenyl or 2-methyl-phenyl;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolsor nitrate; generally X¹ and X² are independently Cl, Br, I or F;typically X¹ and X² are independently Cl;

R^(d) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈ cycloalkyl; generally R^(d) isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically R^(d)is phenyl;

R^(e) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈ cycloalkyl; generally R^(e) isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically R^(e)is phenyl; and

R^(f) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈ cycloalkyl; generally R^(f) isunsubstituted C₁-C₁₀ alkyl, unsubstituted C₆-C₁₀ aryl or unsubstitutedC₆-C₁₀ aryl; typically, R^(f) is phenyl, methyl, p-(OMe)phenyl,iso-propyl or ethyl.

The invention concerns also processes for synthesizing olefin metathesiscatalysts of Formula (B) starting with an olefin metathesis catalyst ofFormula (VIII).

In a typical procedure, as shown in Scheme 5, the PR¹R²R³ ligand of theolefin metathesis catalyst represented by Formula (VIII) can beexchanged with a PR^(g)OR^(h)OR^(i) ligand or a PR^(g)R^(h)OR^(i) ligandat room temperature in an inert solvent, such as dichloromethane ortoluene, wherein:

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R¹ is unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂,—N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₆ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃alkylene)(C₆ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₆ aryl) or unsubstitutedsaturated N-heterocycle;

R⁵ and R⁶ are independently hydrogen, unsubstituted C₅-C₂₄ aryl, orsubstituted C₅-C₂₄ aryl; generally R⁵ and R⁶ are independentlysubstituted C₅-C₂₄ aryl with one to three unsubstituted (C₁-C₆ alkyl)groups or substituted (C₁-C₆ alkyl) groups; typically, R⁵ and R⁶ areindependently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propylphenyl or 2-methyl-phenyl;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolsor nitrate; generally X¹ and X² are independently Cl, Br, I or F;typically X¹ and X² are independently Cl;

R^(g) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈ cycloalkyl; generally R^(g) isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically R^(g)is phenyl;

R^(h) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈ cycloalkyl; generally R^(h) isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically R^(h)is phenyl or methyl; and

R^(i) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl,substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈cycloalkyl or unsubstituted C₃-C₈ cycloalkyl; generally R^(i) isunsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically R^(i)is phenyl or methyl.

In another embodiment, the invention concerns also processes forsynthesizing olefin metathesis catalysts of Formula (C) starting with anolefin metathesis catalyst of Formula (IVa).

In a typical procedure, as shown in Scheme 6, the PR¹R²R³ ligand of theolefin metathesis catalyst represented by Formula (IVa) can be exchangedwith a NHC ligand,

wherein:

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R¹ is unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂,—N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₆ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃alkylene)(C₆ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₆ aryl) or unsubstitutedsaturated N-heterocycle;

R⁵ and R⁶ are independently hydrogen, unsubstituted C₅-C₂₄ aryl, orsubstituted C₅-C₂₄ aryl; generally R⁵ and R⁶ are independentlysubstituted C₅-C₂₄ aryl with one to three unsubstituted (C₁-C₆ alkyl)groups or substituted (C₁-C₆ alkyl) groups; typically, R⁵ and R⁶ areindependently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propylphenyl or 2-methyl-phenyl; and

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolsor nitrate; generally X¹ and X² are independently Cl, Br, I or F;typically X¹ and X² are independently Cl.

In another embodiment, the invention concerns also processes forsynthesizing olefin metathesis catalysts of Formula (C) starting with anolefin metathesis catalyst of Formula (VIII).

In a typical procedure, as shown in Scheme 7, the —PR¹R²R³ ligand of theolefin metathesis catalyst represented by Formula (VIII) can beexchanged with a Grubbs-Hoveyda ligand, wherein:

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R¹ is unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —N(C₁-C₆ alkyl)₂,—N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃ alkylene)(C₆ aryl)]₂;

R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; generally R² is unsubstituted (C₆ aryl),unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —N(C₁-C₆ alkyl)₂, —N(C₁-C₆ alkyl)(C₆ aryl) or —N[(C₁-C₃alkylene)(C₆ aryl)]₂;

R³ is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl),unsubstituted saturated N-heterocycle or substituted saturatedN-heterocycle; generally R³ is unsubstituted (C₆ aryl) or unsubstitutedsaturated N-heterocycle;

R⁵ and R⁶ are independently hydrogen, unsubstituted C₅-C₂₄ aryl, orsubstituted C₅-C₂₄ aryl; generally R⁵ and R⁶ are independentlysubstituted C₅-C₂₄ aryl with one to three unsubstituted (C₁-C₆ alkyl)groups or substituted (C₁-C₆ alkyl) groups; typically, R⁵ and R⁶ areindependently 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl,2-iso-propyl-6-methylphenyl, 2-iso-propylphenyl or 2-methyl-phenyl;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolsor nitrate; generally X¹ and X² are independently Cl, Br, I or F;typically X¹ and X² are independently Cl.

R^(k) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R^(k) ishydrogen;

R^(l) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R^(l) ishydrogen;

R^(m) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R^(m) ishydrogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅, or—NHC(O)OtBu; specifically R^(m) is hydrogen;

R^(n) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃,—NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substitutedhydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, orsubstituted heteroatom-containing hydrocarbyl; typically, R^(n) ishydrogen; and

R^(s) is hydrogen or C₁-C₆ alkyl; typically R^(s) is hydrogen, methyl,ethyl or n-propyl; and

R^(q) is unsubstituted hydrocarbyl, substituted hydrocarbyl; generally,R^(q) is C₁-C₁₀ alkyl; typically, R^(q) is iso-propyl.

At this stage, those skilled in the art will appreciate that manyadditional compounds that fall under the scope of the invention can beprepared by performing various common chemical reactions. Details ofcertain specific chemical transformations are provided in the examples.

For example, the olefin metathesis catalysts are typically added to aresin composition as a solid, a solution, or as a suspension. When theolefin metathesis catalysts are added to a resin composition as asuspension, the olefin metathesis catalysts are suspended in adispersing carrier such as mineral oil, paraffin oil, soybean oil,tri-iso-propylbenzene, or any hydrophobic liquid which has asufficiently high viscosity so as to permit effective dispersion of thecatalyst(s), and which is sufficiently inert and which has asufficiently high boiling point so that is does not act as a low-boilingimpurity in the olefin metathesis reaction.

Olefins

Resin compositions that may be used with the present invention disclosedherein comprise one or more cyclic olefins. Such cyclic olefins may beoptionally substituted, optionally heteroatom-containing,mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefinmay generally be any strained or unstrained cyclic olefin, provided thecyclic olefin is able to participate in a ROMP reaction eitherindividually or as part of a ROMP cyclic olefin composition.

Examples of bicyclic and polycyclic olefins thus include, withoutlimitation, dicyclopentadiene (DCPD); trimer and other higher orderoligomers of cyclopentadiene including without limitationtricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer,and cyclopentadiene pentamer; ethylidenenorbormene; dicyclohexadiene;norbornene; C₂-C₁₂ hydrocarbyl substituted norbornenes;5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene;5-decyl-2-norbomene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbomene;5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene;5-propenyl-2-norbornene; 5-butenyl-2-norbornene; 5-tolyl-norbornene;5-methyl-2-norbomene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene;5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene;5-acetylnorbornene; 5-methoxycarbonylnorbornene;5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbomene;bicyclo[2.2.1]hept-2-ene-2-carboxylic acid, 2-ethylhexyl ester;5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene;cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene;2,3-dimethoxynorbornene; norbomadiene; tricycloundecene;tetracyclododecene; 8-methyl tetracyclododecene;8-ethyltetracyclododecene; 8-methoxy carbonyltetracyclo dodecene;8-methyl-8-tetra cyclododecene; 8-cyanotetracyclo dodecene;pentacyclopentadecene; pentacyclo hexadecene;bicyclo[2.2.1]hept-2-ene-5-phenoxymethyl; 2-ethylhexylester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; 2-hydroxyethylester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid;bicyclo[2.2.1]hept-5-ene-2-methanol;bicyclo[2.2.1]hept-5-ene-2-heptanoic acid-methyl ester;bicyclo[2.2.1]hept-5-ene-2-hexanoic acid-methyl ester;1,4:5,8-dimethanonaphthalene, 2-hexyl-1,2,3,4,4a,5,8, 8a-octahydro;bicyclo[2.2.1]hept-5-ene-2-octanoic acid-methyl ester; 1,4:5,8-dimethanonaphthalene; 2-butyl-1,2,3,4,4a,5,8,8a-octahydro;ethylidenetetracyclododecene;2-vinyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethano naphthalene; andthe like, and their structural isomers, stereoisomers, and mixturesthereof.

EXPERIMENTAL General Information—Materials and Methods

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g., amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. The examplesare to be considered as not being limiting of the invention describedherein.

All reactions involving metal complexes were conducted in oven-driedglassware under an argon or nitrogen atmosphere using standard Schlenktechniques. Chemicals and solvents were obtained from Sigma-Aldrich,Strem, Alfa Aesar, Nexeo, Brenntag, AG Layne and TCI. Commerciallyavailable reagents were used as received unless otherwise noted. Silicagel was purchased from Fisher (0.040-0.063 μm, EMD Millipore). Solventswere dried by passing through an activated alumina column (n-pentane,benzene, toluene, Et₂O, and THF).

SIMes.HBr, SIMes.HCl, SIPr.HCl, P426, P510,1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene andCatalysts C959, C931, C848, C831, C949, C601, C727, C787, and C765 wereprepared using known methods.

The crystallographic measurements were performed at 100(2) K using aBruker APEX-II CCD area detector diffractometer (Mo—K_(α) radiation,λ=0.71073 Å). In each case, a specimen of suitable size and quality wasselected and mounted onto a nylon loop. The structures were solved bydirect methods, which successfully located most of the nonhydrogenatoms. Semi-empirical absorption corrections were applied. Subsequentrefinement on F² using the SHELXTL/PC package (version 6.1) allowedlocation of the remaining non-hydrogen atoms. Depending on theexperimental conditions, some of the olefin metathesis catalysts of theinvention were obtained as solvates.

Ultrene® 99 dicyclopentadiene (DCPD) was obtained from CymetechCorporation. A modified DCPD base resin containing 20-25%tricyclopentadiene (and small amounts of higher cyclopentadienehomologs) (DCPD-HT) was prepared by heat treatment of Ultrene® 99 DCPDgenerally as described in U.S. Pat. No. 4,899,005.

¹H and ¹³C NMR spectra were recorded on a Varian 400 MHz spectrometer.Chemical shifts are reported in ppm downfield from Me₄Si by using theresidual solvent peak as an internal standard (CDCl₃—δ 7.24 ppm;CD₂Cl₂—δ 5.32 ppm). ³¹P NMR used an external standard of 85% H₃PO₄,referenced to 0 ppm. Spectra were analyzed and processed usingMestReNova software. Deuterated solvents were purchased from CambridgeIsotopes Laboratories, Inc. and were degassed and stored over activated3 Å molecular sieves prior to use.

The following abbreviations are used in the examples:

mL milliliter L liter ° C. degrees Celsius CD₂Cl₂ deuterateddichloromethane CDCl₃ deuterated chloroform C₆D₆ deuterated benzeneSIMes•HBr N,N′-bis-(2,4,6-trimethylphenylamino)ethane dihydrobromideSIMes•HCl N,N′-bis-(2,4,6-trimethylphenylamino)ethane dihydrochlorideSIPr•HCl 1,3-bis(2,6-di-iso-propylphenyl)-4,5-dihydroimidazoliumchloride Ar argon HCl hydrochloric acid KHMDS potassiumbis(trimethylsilyl)amide r.t. room temperature C765

Dichloro(3-methyl-2-butenylidene)bis(triphenylphosphine) ruthenium [CAS191609-95-7] C727

[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)bis(pyridine)-Ruthenium [CAS 357186-58-4] 1,3-Bis(2,4,6- trimethyl- phenyl)- 4,5- dihydro- imidazol- 2-ylidene

C959 (PPh₃)₃Ru(Cl)₂ tris(triphenylphosphine)ruthenium(II) dichloride[CAS 15529-49-4] (2-Me)THF 2-methyltetrahydrofuran THF tetrahydrofuranC787

Benzylidenedichlorobis(triphenylphosphine)ruthenium [CAS 172222-26-3]C848

Dichloro[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine) ruthenium (II)[CAS 246047-72-3] C831

Dichloro[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(triphenylphosphine) ruthenium (II)[CAS 357261-84-8] PTSA p-Toluenesulfonic acid C931

[1,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(phenylindenylidene)(triphenylphosphine)ruthenium(II) [CAS 340810-50-6]C949

[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylindenylidene)(tricyclohexylphosphine)ruthenium(II) [CAS 536724-67-1] C601

Dichloro(2-isopropoxyphenylmethylene) (tricyclohexylphosphine)ruthenium(II) [CAS 203714-71-0] P426

1,3-Bis(2,4,6-trimethylphenyl)-2- (trichloromethyl)imidazolidine [CAS260054-47-5] P510

1,3-bis[2,6-bis(1-methylethyl)phenyl]-2-(trichloromethyl) imidazolidine[CAS 465543-05-9]

EXAMPLES Example 1 Synthesis of C973

In a 3 L, 3-neck round bottom flask were added C959 (100.0 g, 104.2mmol), 1,1-diphenyl-2-propyn-1-ol (24.9 g, 119.8 mmol), andtriphenylphosphine (27.3 g, 104.2 mmol) under air. The flask wasequipped with a thermocouple and rubber suba-seal septum and then it wasplaced under Ar using Schlenk technique. The reagents and products ofthis reaction are highly air sensitive in solution. A 1 L additionfunnel was attached to the flask under a flow of Ar. To the additionfunnel were added (2-Me)THF (1 L) and 4 M HCl (25.6 mL, 104.2 mmol) indioxane using Schlenk technique. The solution was added over 10 minutesat room temperature with stirring. Another 0.75 L (2-Me)THF were addeddirectly to the flask. The addition funnel was replaced with a glassstopper under a flow of Ar and the flask was lowered into a pre-heatedoil bath at 65° C. The reaction was monitored by ³¹P NMR. Whenconversion was deemed to be complete, the reaction flask was removedfrom the oil bath and hot filtered via cannula transfer through a celitepad (in an evacuated Schlenk filter) into a Schlenk flask. Approximately85% (2-Me)THF was removed at room temperature (water bath) under vacuum.The resulting slurry was cooled to 0° C. then filtered on a coarse glassfrit under air. The solid was washed quickly with 3×50 mL portions of 0°C. (2-Me)THF followed by hexanes (200 mL) (r.t.) and 2-propanol (100mL). The solid from the frit was re-slurred with hexanes (200 mL) andfiltered again. The solid was air-dried until no condensation was seenon the outside of the glass frit, then transferred to a 200 mL roundbottom flask and dried under high vacuum overnight. The final ¹H NMR and³¹P NMR in CDCl₃ indicate that the complex is a 1:1 adduct of(PPh₃)₂Ru(PhInd)Cl₂, and (2-Me)THF, C973, for a final molecular weightof 973 g/mol. Yield=74.1 g (73%).

¹H NMR (400 MHz in CDCl₃ at r.t.): 67 =7.2-7.6 (overlapping CDCl₃ andaromatics), 7.07 (d, Ind, 1H), 6.62 (t, Ind, 1H), 6.43 (s, Ind, 1H),3.92 (m, (2-Me)THF, 2H), 3.70 (m, (2-Me)THF, 1H), 1.88-1.98 (overlappingm, (2-Me)THF, 3H), 1.41 (m, (2-Me)THF, 1H), 1.23 (d, (2-Me)THF, 3H).

Example 2 Synthesis of C905

To a 40 mL scintillation vial equipped with a magnetic stir bar wereadded C973 (0.750 mg, 0.771 mmol), Ph₂P[N(C₂H₄)₂O] ([CAS 13743-27-6]0.837 g, 3.08 mmol), and diethyl ether (20 mL). The suspension wasallowed to stir for 14 hours at ambient temperature. The resultingprecipitate was isolated by filtration, washed with diethyl ether (5 mL)followed by diethyl ether/hexanes (1:1, 10 mL), then dried in vacuum toafford C905 as a red/brown powder (0.507 g, 72.7% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 7.71 (m, 6H), 7.61-7.50 (m, 4H), 7.48-7.40(m, 5H), 7.40-7.31 (m, 11H), 7.24 (d, J=7.4 Hz, 2H), 6.79 (t, J=7.4 Hz,1H), 6.38 (s, 1H), 3.42 (br s, 8H), 2.81 (br s, 8H). ³¹P NMR (162 MHz,CD₂Cl₂) δ 79.3 (s).

Example 3 Synthesis of C940

To a 40 mL scintillation vial equipped with a magnetic stir bar wereadded C905 (0.200 mg, 0.221 mmol),1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (0.071 g,0.23 mmol), and toluene (10 mL). The resulting solution was stirred for2 hours, devolatilized, and the resulting residue recrystallized fromtoluene/pentane at −35° C. The resulting brown crystals were separatedby filtration and dried in vacuum affording C940 (0.146 g, 70.1% yield).FIG. 1 shows the ORTEP diagram of C940.

¹H NMR (400 MHz, CD₂Cl₂) δ 7.78 (d, J=7.6 Hz, 1H), 7.56-7.33 (m, 7H),7.27 (t, J=7.3 Hz, 1H), 7.24-7.11 (m, 6H), 7.08-7.01 (m, 2H), 6.98 (d,J=6.5 Hz, 3H), 6.93 (t, J=7.6 Hz, 1H), 6.54 (s, 1H), 6.39 (s, 1H), 6.00(s, 1H), 4.07-3.97 (m, 2H), 3.90-3.71 (m, 2H), 3.37-3.22 (m, 4H), 2.65(s, 6H), 2.62-2.48 (m, 4H), 2.38 (s, 3H), 2.12 (s, 3H), 1.97 (s, 3H),1.81 (s, 3H). ³¹P NMR (162 MHz, CD₂Cl₂) δ 76.3 (s).

Example 4 Synthesis of C923

To a 20 mL scintillation vial equipped with a magnetic stir bar wereadded C973 (0.500 mg, 0.514 mmol),4,4′-(phenylphosphinidene)bismorpholine ([CAS 13337-35-4] 0.576 g, 2.06mmol), and diethyl ether (10 mL). The suspension was allowed to stir for14 hours at ambient temperature. The resulting precipitate was isolatedby filtration, washed with diethyl ether (5 mL) followed by diethylether/hexanes (1:1, 10 mL) and hexanes (10 mL), then dried in vacuum toafford C923 as a red/brown powder (0.313 g, 66.0% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 7.95-7.15 (m, 18H), 7.15-6.30 (m, 2H), 3.49(br s, 16H), 3.02 (br s, 16H). ³¹P NMR (162 MHz, CD₂Cl₂) δ 97.3 (br s).

Example 5 Synthesis of C949

To a 20 mL scintillation vial equipped with a magnetic stir bar wereadded SIMes.HBr (0.110 mg, 0.285 mmol), KHMDS (0.057 g, 0.285 mmol), andtoluene (2 mL). The resulting reaction was allowed to stir for 30minutes at ambient temperature, then it was filtered through a pad ofcelite, and combined with C923 and hexanes (8 mL) in a 20 mLscintillation vial equipped with a magnetic stir bar. The resultingsuspension was subsequently stirred for 6 hours at ambient temperature.The resulting precipitate was isolated by filtration, washed withtoluene/hexanes (3:7, 2×10 mL) followed by hexanes (10 mL) then dried invacuum, to afford C949 as a red/brown powder (0.239 g, 93.0% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 7.91 (d, J=7.3 Hz, 1H), 7.66 (d, J=7.6 Hz,2H), 7.56 (t, J=6.9 Hz, 1H), 7.42 (t, J=7.6 Hz, 2H), 7.25 (t, J=7.3 Hz,1H), 7.21-7.07 (m, 3H), 7.09-6.93 (m, 6H), 6.54 (s, 1H), 6.38 (s, 1H),5.96 (s, 1H), 4.10-3.97 (m, 2H), 3.90-3.70 (m, 2H), 3.29 (br s, 4H),3.26-3.03 (m, 4H), 2.96-2.80 (m, 4H), 2.78-2.69 (m, 4H), 2.67 (s, 3H),2.66 (s, 3H), 2.38 (s, 3H), 2.13 (s, 3H), 1.97 (s, 3H), 1.76 (s, 3H).³¹P NMR (162 MHz, CD₂Cl₂) δ 97.4 (s).

Example 6 Synthesis of C941

To a 40 mL scintillation vial equipped with a magnetic stir bar wereadded C973 (1.00 g, 1.03 mmol), 4,4″,4″′-phosphinidyltrismorpholine([CAS 5815-61-2] 1.19 g, 4.11 mmol), and diethyl ether (30 mL). Thesuspension was allowed to stir for 14 hours at ambient temperature. Theresulting precipitate was isolated by filtration, washed with diethylether (4×15 mL) followed by hexanes (2×10 mL), then dried in vacuum toafford C941 as a red powder (0.740 g, 76.5% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 8.61-8.44 (m, 1H), 7.87-7.72 (m, 2H), 7.60(t, J=7.0 Hz, 1H), 7.45 (t, J=7.4 Hz, 3H), 7.40-7.20 (m, 3H), 3.52 (s,24H), 3.15 (s, 24H). ³¹P NMR (162 MHz, CD₂Cl₂) δ 100.1 (br s).

Example 7 Synthesis of C958

To a 20 mL scintillation vial equipped with a magnetic stir bar wasadded C941 (0.500 g, 0.531 mmol),1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (0.171 g,0.558 mmol), and diethyl ether (10 mL). The resulting suspension wasallowed to stir for 8 hours at ambient temperature. The resultingprecipitate was isolated by filtration, washed with diethyl ether (2×10mL) followed by hexanes (10 mL) then dried in vacuum to afford C958 as ared/brown powder (0.434 g, 85.3% yield). FIG. 2 shows the ORTEP diagramof C958.

¹H NMR (400 MHz, CD₂Cl₂) δ 8.41 (d, J=7.4 Hz, 1H), 7.70 (d, J=7.8 Hz,2H), 7.54 (t, J=7.4 Hz, 1H), 7.43 (t, J=7.5 Hz, 2H), 7.30-7.20 (m, 2H),7.14 (t, J=7.5 Hz, 2H), 7.09-6.98 (m, 3H), 6.42 (s, 1H), 5.99 (s, 1H),4.07-3.97 (m, 2H), 3.91-3.72 (m, 2H), 3.23 (s, 12H), 2.79 (s, 12H), 2.71(s, 3H), 2.67 (s, 3H), 2.36 (s, 3H), 2.17 (s, 3H), 2.10 (s, 3H), 1.81(s, 3H). ³¹P NMR (162 MHz, CD₂Cl₂) δ 108.8 (s).

Example 8 Synthesis of C1042

To a 20 mL scintillation vial equipped with a magnetic stir bar wasadded 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolium chloride(0.238 g, 0.558 mmol), potassium bis(trimethylsilyl)amide (0.111 g,0.558 mmol), and toluene (5 mL). The resulting reaction was allowed tostir for 30 minutes at ambient temperature, filtered through a pad ofcelite, and combined with C941 (0.500 g, 0.531 mmol) and heptanes (15mL) in a 40 mL scintillation vial equipped with a magnetic stir bar. Theresulting suspension was subsequently stirred for 3 hours at ambienttemperature. The resulting precipitate was isolated by filtration,washed with toluene/heptanes (1:4, 2×10 mL) followed by heptanes (10 mL)then dried in vacuum to afford C1042 (0.436 g, 78.7% yield) as ared/brown powder.

¹H NMR (400 MHz, CDCl₃) δ 8.66 (d, J=7.4 Hz, 1H), 7.64 (d, J=8.3 Hz,2H), 7.53-7.42 (m, 2H), 7.37 (t, J=6.5 Hz, 4H), 7.23 (t, J=7.5 Hz, 1H),7.12 (t, J=7.5 Hz, 1H), 7.04 (d, J=7.2 Hz, 1H), 6.94 (s, 1H), 6.73-6.67(m, 2H), 6.61-6.56 (m, 1H), 4.27-4.18 (m, 1H), 4.17-3.91 (m, 4H),3.91-3.81 (m, 1H), 3.59-3.49 (m, 1H), 3.31-3.18 (m, 12H), 3.19-3.10 (m,1H), 2.93-2.77 (m, 6H), 2.75-2.63 (m, 6H), 1.58 (d, J=6.4 Hz, 3H), 1.53(d, J=6.4 Hz, 3H), 1.37 (d, J=6.6 Hz, 3H), 1.26 (d, J=6.8 Hz, 3H), 1.22(d, J=6.8 Hz, 3H), 1.09 (d, J=6.8 Hz, 3H), 0.94 (d, J=6.8 Hz, 3H), 0.82(d, J=6.6 Hz, 3H). ³¹P NMR (162 MHz, CDCl₃) δ 102.8 (s).

Example 9 Synthesis of C1050

To a 20 mL scintillation vial equipped with a magnetic stir bar wereadded SIMes.HBr (0.173 mg, 0.446 mmol), KHMDS (0.089 g, 0.446 mmol), andtoluene (4 mL). The resulting reaction was allowed to stir for 30minutes at ambient temperature, then filtered through a pad of celite,and combined with C941 (0.400 g, 0.425 mmol) and hexanes (16 mL) in a 40mL scintillation vial equipped with a magnetic stir bar. The resultingsuspension was subsequently stirred for 4 hours at ambient temperature.The resulting precipitate was isolated by filtration, washed withtoluene/hexanes (1:5, 2×10 mL) followed by hexanes (10 mL) then dried invacuum to afford C1050 as a red/brown powder (0.406 g, 91.0% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 8.41 (d, J=7.5 Hz, 1H), 7.70 (d, J=7.8 Hz,2H), 7.54 (t, J=7.2 Hz, 1H), 7.43 (t, J=7.6 Hz, 2H), 7.30-7.20 (m, 4H),7.20-7.10 (m, 4H), 7.09-6.98 (m, 3H), 6.42 (s, 1H), 5.99 (s, 1H),4.07-3.97 (m, 2H), 3.91-3.72 (m, 2H), 3.24 (s, 12H), 2.79 (s, 12H), 2.71(s, 3H), 2.67 (s, 3H), 2.36 (s, 3H), 2.34 (s, 3H), 2.17 (s, 3H), 2.10(s, 3H), 1.81 (s, 3H). ³¹P NMR (162 MHz, CD₂Cl₂) δ 108.9 (s).

Example 10 Synthesis of C947

To a 20 mL scintillation vial equipped with a magnetic stir bar wereadded C1050 (0.300 g, 0.286 mmol), phenoxydiphenylphosphine ([CAS13360-92-4] 0.057 g, 0.300 mmol), PTSA (0.169 g, 0.886 mmol) and toluene(5 mL). The resulting reaction was allowed to stir for 60 minutes atambient temperature, then it was filtered through a plug of silica gel,devolatilized and the resulting residue was recrystallized fromtoluene/heptanes at −35° C. The red/brown crystals were isolated byfiltration, washed with toluene/heptanes (1:5, 2×10 mL) followed byheptanes (5 mL) then dried in vacuum to afford C947 (0.228 g, 84.2%yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 8.18 (d, J=7.5 Hz, 1H), 7.58 (d, J=7.7 Hz,2H), 7.54 (t, J=7.4 Hz, 1H), 7.40 (t, J=7.6 Hz, 2H), 7.27-7.11 (m, 7H),7.08-7.00 (m, 7H), 6.97 (d, J=7.3 Hz, 1H), 6.82 (t, J=7.8 Hz, 2H), 6.71(t, J=7.3 Hz, 1H), 6.63 (s, 1H), 6.54 (d, J=8.3 Hz, 2H), 6.45 (s, 1H),6.07 (s, 1H), 4.19-4.04 (m, 2H), 4.00-3.78 (m, 2H), 2.71 (s, 3H), 2.67(s, 3H), 2.43 (s, 3H), 2.26 (s, 3H), 1.99 (s, 3H), 1.79 (s, 3H). ³¹P NMR(162 MHz, CD₂Cl₂) δ 127.9 (s).

Example 11 Synthesis of C609

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C601 (0.500 g, 0.833 mmol), 4,4″,4″′-phosphinidyntrismorpholine([CAS 5815-61-2] 0.361 g, 1.25 mmol), and diethyl ether (20 mL). Theresulting reaction was allowed to stir for 4 hours at 35° C. then cooledto ambient temperature. The resulting precipitate was isolated byfiltration, washed with diethyl ether (2×10 mL), and dried in vacuum toafford C609 (0.420 g, 82.8% yield) as a pale red/brown powder.

¹H NMR (400 MHz, C₆D₆) δ 16.69 (d, J=5.0 Hz, 1H), 7.36 (d, J=7.4 Hz,1H), 7.20 (t, J=7.4 Hz, 1H), 6.82 (t, J=7.4 Hz, 1H), 6.59 (d, J=8.2 Hz,1H), 4.81-4.70 (m, 1H), 3.52 (br s, 12H), 3.10 (br s, 12H), 1.72 (d,J=6.1 Hz, 6H). ³¹P NMR (162 MHz, C₆D₆) δ 120.3 (s). ³¹P NMR (162 MHz,CD₂Cl₂) δ 119.7 (s).

Example 12 Synthesis of C591

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C601 (0.500 g, 0.833 mmol), 4-(diphenylphosphino)morpholine (0.294g, 1.08 mmol), and diethyl ether (20 mL). The resulting reaction wasallowed to stir for 4 hours at 30° C. The resulting precipitate wasisolated by filtration, washed with diethyl ether (2×10 mL), and driedin vacuum to afford C591 (0.302 g, 61.4% yield) as a pale red/brownpowder.

¹H NMR (400 MHz, CDCl₃) δ 16.62 (d, J=5.8 Hz, 1H), 7.82-7.70 (m, 4H),7.61 (t, J=7.8 Hz, 1H), 7.56 (d, J=7.6 Hz, 1H), 7.52-7.39 (m, 6H), 7.16(d, J=8.5 Hz, 1H), 7.08 (t, J=7.5 Hz, 1H), 5.43-5.33 (m, 1H), 3.75-3.62(m, 4H), 3.18 (m, 4H), 1.85 (d, J=6.1 Hz, 6H). ³¹P NMR (162 MHz, CDCl₃)δ 109.5 (s).

Example 13 Synthesis of C600

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C601 (0.500 g, 0.833 mmol),4,4′-(phenylphosphinidene)bismorpholine (0.303 g, 1.08 mmol), anddiethyl ether (20 mL). The resulting reaction was allowed to stir for 4hours at 30° C. The resulting precipitate was isolated by filtration,washed with diethyl ether (2×10 mL), and dried in vacuum to afford C600(0.422 g, 84.4% yield) as a pale red/brown powder.

¹H NMR (400 MHz, CDCl₃) δ 16.59 (d, J=5.2 Hz, 1H), 7.86-7.76 (m, 2H),7.61 (t, J=8.0 Hz, 1H), 7.55 (d, J=7.6 Hz, 1H), 7.50-7.40 (m, 3H), 7.15(d, J=8.4 Hz, 1H), 7.08 (t, J=7.6 Hz, 1H), 5.41-5.30 (m, 1H), 3.80-3.60(m, 8H), 3.41-3.29 (m, 4H), 3.26-3.15 (m, 4H), 1.84 (d, J=6.2 Hz, 6H).³¹P NMR (162 MHz, CDCl₃) δ 125.9 (br s).

Example 14 Synthesis of C590

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C601 (0.500 g, 0.833 mmol), 1-(diphenylphosphino)piperidine ([CAS22859-54-7] 0.292 g, 1.08 mmol), and diethyl ether (20 mL). Theresulting reaction was allowed to stir for 14 hours at 30° C. Theresulting precipitate was isolated by filtration, washed with diethylether (2×10 mL), and then dissolved in a minimal amount ofdichloromethane (4 mL). The solution was filtered through a pad ofcelite then hexanes (30 mL) was slowly added to afford a redprecipitate. The solid was isolated by filtration, washed with hexanes(2×10 mL), and dried in vacuum to afford C590 (0.191 g, 38.9% yield) asa red solid.

¹H NMR (400 MHz, CDCl₃) δ 16.70 (d, J=5.7 Hz, 1H), 7.80-7.70 (m, 4H),7.59 (t, J=7.8 Hz, 1H), 7.55 (d, J=7.7 Hz, 1H), 7.50-7.37 (m, 6H), 7.15(d, J=8.4 Hz, 1H), 7.07 (t, J=7.5 Hz, 1H), 5.42-5.31 (m, 1H), 3.20-3.08(m, 4H), 1.86 (d, J=6.1 Hz, 6H), 1.66-1.50 (m, 6H). ³¹P NMR (162 MHz,CDCl₃) δ 107.9 (s).

Example 15 Synthesis of C627 from C591

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C591 (0.250 g, 0.423 mmol), P426 (0.216 g, 0.507 mmol), and 10%toluene/heptanes (v/v) (10 mL). The resulting reaction was heated to 90°C. for 5 hr. The resulting precipitate was isolated by filtration,washed with hexanes (2×10 mL) followed by methanol (2×10 mL), then driedin vacuum to afford C627 (0.146 g, 55.0% yield) as a green solid. TheNMR data correspond to the data reported in the literature.

Example 16 Synthesis of C627 from C1050

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C1050 (0.5 g, 0.5 mmol), 2-isopropoxy--methylstyrene (0.18 g, 1.02mmol), DCM (5 mL), and tosyl chloride (0.11 g, 0.57 mmol). The resultingreaction was heated to 60° C. for 30 min and then concentrated todryness. The material was triturated with methanol (10 mL) and theresulting green solid was collected on a fritted funnel and washed withmethanol (10 mL) followed by hexanes (10 mL) then dried in vacuum toafford C627 (0.268 g, 90% yield) as a green solid. The NMR datacorrespond to the data reported in the literature.

Example 17 Synthesis of C627 from C940

To a 40 mL scintillation vial equipped with a magnetic stirbar was addedC940 (0.5 g, 0.53 mmol), 2-iso-propoxy-β-methylstyrene (0.18 g, 1.02mmol), EtOAc (20 mL), and tosyl chloride (0.11 g, 0.58 mmol). Theresulting reaction was heated to 60° C. for 30 min and then concentratedto dryness. The material was triturated with methanol (10 mL) and theresulting green solid was collected on a fritted funnel and washed withmethanol (10 mL) followed by hexanes (10 mL) then dried in vacuum toafford C627 (0.177 g, 53% yield) as a green solid. The NMR datacorresponded to the data reported in the literature.

Example 18 Synthesis of C627 from C609

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C609 (1.0 g, 1.64 mmol), P426 (0.805 g, 1.89 mmol), and 10%toluene/heptanes (v/v) (10 mL). The resulting reaction was heated to 90°C. for 3 hr. The resulting precipitate was isolated by filtration anddissolved in DCM (10 mL). PTSA (0.343 g) was added to the solution andallowed to stir at room temperature for 30 min. The reaction mixture wasconcentrated and the C627 was triturated with MeOH (10 mL). Theresulting precipitate was collected on a fritted funnel and washed withmethanol (10 mL), then dried in vacuum to afford C627 (0.74 g, 72%yield) as a green solid. The NMR data corresponded to the data reportedin the literature.

Example 19 Synthesis of C711 from C591

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C591 (0.250 g, 0.423 mmol), P510 (0.259 g, 0.507 mmol), and 10%toluene/heptanes (v/v) (10 mL). The resulting reaction was heated to 90°C. for 5 hr. The resulting precipitate was isolated by filtration,washed with hexanes (2×10 mL) followed by methanol (2×10 mL), then driedin vacuum to afford C711 (0.224 g, 74.5% yield) as a green solid. TheNMR data corresponded to the data reported in the literature.

Example 20 Synthesis of C627 from C609

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded C609 (1.0 g, 1.64 mmol), P510 (1.0 g, 1.96 mmol), and 10%toluene/heptanes (v/v) (10 mL). The resulting reaction was heated to 90°C. for 5 hr. The resulting precipitate was isolated by filtration,washed with hexanes (2×10 mL) followed by methanol (2×10 mL), then driedin vacuum to afford C711 (0.64 g, 54.8% yield) as a green solid. The NMRdata corresponded to the data reported in the literature.

Example 21 Synthesis of C829

To a THF solution (5 mL) of C787 (215 mg, 0.273 mmol) was added a THFsolution (3 mL) of Cy₂P(morph) (309.8 mg, 1.093 mmol) at r.t. Themixture was allowed to stir at ambient temperature for 15 min, leadingto the quantitative formation of C829 as monitored in situ by ³¹P NMRspectroscopy. The solvent was then removed under reduced pressure toafford a sticky solid. To this solid was added n-pentane (3×10 mL), andthe resulting solid was removed by filtration. The combined n-pentanesolutions were slowly concentrated by vapor diffusion intohexamethyldisiloxane at r.t. over 12 h, affording purple crystals ofC829 (80 mg, 35%) which were isolated by filteration, washed with coldn-pentane, and dried under vacuum. FIG. 9 shows the ORTEP diagram ofC829.

¹H NMR (300 MHz; C₆D₆): δ 20.52 (s, 1H), 8.47 (d, 2H, J_(H-H)=10.6 Hz),7.16 (t, 1H, J_(H-H)=7.2 Hz), 7.00 (t, 2H, J_(H-H)=7.5 Hz), 3.53 (t, 8H,J_(H-H)=3.8 Hz), 2.82-2.76 (m, 8H), 1.98-1.12 (m, 44H). ³¹P NMR (121MHz; C₆D₆): δ 95.7 (s).

Example 22 Synthesis of C852

To a toluene solution (2 mL) of SIMes-HCl (34.7 mg, 0.101 mmol) wasadded solid KHMDS (20.2 mg, 0.101 mmol). The resulting mixture wasallowed to stir at r.t. for 15 min, and then transferred into a toluenesolution (5 mL) of C829 (79.8 mg, 0.096 mmol). The reaction was warmedup to 65° C. for 12 h. The resulting suspension was then passed througha short plug of Celite to remove the unwanted solid. All volatiles wereremoved under reduced pressure, affording a brown solid which was washedwith cold n-pentane (10 mL). Further recrystallization from THF/pentaneyielded brown/pink crystals of C852 (50 mg, 61%). FIG. 3 shows the ORTEPdiagram of C852.

¹H NMR (300 MHz; C₆D₆): δ 19.56 (s, 1H), 9.13 (bs, 2H), 7.11-6.90 (m,5H), 6.10 (bs, 2H), 3.45 (t, 4H, J_(H-H)=4.3 Hz), 3.31-0.75 (m, 48H).³¹P NMR (121 MHz; C₆D₆): δ 92.2 (s).

Example 23 Synthesis of C807

To a THF solution (6 mL) of C765 (250 mg, 0.327 mmol) was added a THFsolution (6 mL) of Cy₂P(morph) (370.6 mg, 1.308 mmol) at ambienttemperature. The mixture was allowed to stir at ambient temperature for15 min, leading to the quantitative formation of C807 as monitored insitu by ³¹P NMR spectroscopy. The solvent was then removed under reducedpressures to afford a brown oil. To this oil was added n-pentane (45mL). The mixture was stirred at r.t. for 30 min, and the resulting solidwas removed by filtration. The n-pentane solution was concentrated to˜20 mL, and allowed to stand at −30° C. for 12 h, affording purplecrystals of C807 (74 mg, 28%) which were isolated by filteration, washedwith cold n-pentane, and dried under vacuum.

¹H NMR (300 MHz; C₆D₆): δ 19.81 (d, 1H, J_(H-H)=11.2 Hz), 8.08 (d, 1H,J_(H-H)=11.2 Hz), 3.60 (t, 8H, J_(H-H)=3.7 Hz), 2.94 (t, 8H, J_(H-H)=3.7Hz), 2.07-0.91 (m, 54H). ³¹P NMR (121 MHz; C₆D₆): δ 95.3 (s).

Example 24 Synthesis of C830

To a THF solution (2 mL) of C807 (50 mg, 0.062 mmol) was added a THFsolution (2 mL) of SIMes-CHCl₃ (26.4 mg, 0.062 mmol). The reaction waswarmed up to 65° C. for 2 h. During the course of the reaction, thecolor changed from purple to brown. All volatiles were removed underreduced pressures, affording a brown solid. To this solid was addedn-pentane (3×10 mL), and the resulting solid was removed by filtration.The combined n-pentane solution was slowly concentrated by vapordiffusion into hexamethyldisiloxane at r.t. over 12 h, affording browncrystals of C830 (18 mg, 35%) which were isolated by filteration, washedwith Et₂O, and dried under vacuum.

¹H NMR (300 MHz; C₆D₆): δ 19.03 (d, 1H, J_(H-H)=11.3 Hz), 7.68 (d, 1H,J_(H-H)=11.3 Hz), 6.85 (s, 2H), 6.57 (s, 2H), 3.53 (t, 4H, J_(H-H)=2.9Hz), 2.74 (s, 6H), 2.50 (s, 6H), 2.15 (s, 3H), 1.97 (s, 3H), 1.07-0.92(m, 36H). ³¹P NMR (121 MHz; C₆D₆): δ 90.3 (s).

Example 25 Synthesis of C803

To a THF solution (3 mL) of C765 (100 mg, 0.131 mmol) was added a THFsolution (3 mL) of Cy₂P(O^(i)Pr) ([CAS 65796-69-2]134.1 mg, 0.523 mmol)at ambient temperature. The mixture was allowed to stir at ambienttemperature for 15 min, leading to the quantitative formation of thebis-phosphinite complex as monitored in situ by ³¹P NMR spectroscopy(143.6 ppm). To this solution was added a THF solution (2 mL) ofSIMes-CHCl₃ (55.7 mg, 0.131 mmol). The resulting mixture was allowed toreflux at 65° C. for 2 h. The solvent was then removed under reducedpressures to afford a brown solid. To this solid was added n-pentane (10mL). The mixture was stirred at r.t. for 5 min, and the resulting solidwas removed by filtration. Slow evaporation of the n-pentane filtrateafforded brown crystals of C803 (71 mg, 68%) which were isolated byfilteration, washed with cold n-pentane, and dried under vacuum. FIG. 4shows the ORTEP diagram of C803.

¹H NMR (300 MHz; C₆D₆): δ 18.94 (d, 1H, J_(H-H)=11.2 Hz), 7.57 (d, 1H,J_(H-H)=11.2 Hz), 6.84 (s, 2H), 6.58 (s, 2H), 3.24-3.15 (m, 3H), 2.77(s, 6H), 2.50 (s, 6H), 2.12 (s, 3H), 1.98 (s, 3H), 1.66-0.90 (m, 18H).³¹P NMR (121 MHz; C₆D₆): δ 151.0 (s).

Example 26 Synthesis of Olefin Metathesis Catalysts Represented byFormula (XI)

To a THF solution (2 mL) of the bispyridine complex C727 (100 mg, 0.138mmol) was added 1.2 equivalent (0.165 mmol) of the corresponding PR¹R²R³ligand of Formula (II) in THF (1 mL). The resulting mixture was stirredat r.t. for 20 min. All volatiles were then removed under reducedpressures. Addition of pentane or diethyl ether led to a pinkprecipitate of the desired complex which was isolated by filtration anddried under vacuum.

The olefin metathesis catalysts synthesized according to the proceduredescribed in Example 26 are disclosed in Table 6. FIGS. 5, 6, 7, and 8show the ORTEP diagrams of C850, C825, C832, and C865, respectively.

TABLE 6 Olefin metathesis catalyst

Quantity (mg) Yield (%) δ ¹H NMR (300 MHz; C₆D₆) δ ³¹P NMR (121 MHz;C₆D₆) C852

110 94 19.56 (s, 1H), 9.13 (bs, 2H), 7.11-6.90 (m, 5H), 6.10 (bs, 2H),3.45 (t, 4H, J_(H—H) = 4.3 Hz), 3.31-0.75 (m, 48H) 92.2 (s) C855

79 67 19.30 (s, 1H), 8.03 (bs, 2H), 7.10-6.88 (m, 5H), 6.17 (bs, 2H),3.27 (t, 16H, J_(H—H) = 3.8 Hz), 2.75 (s, 6H), 2.69- 2.67 (m, 12H), 2.35(s, 6H), 1.77 (s, 3H). 131.9 (s) C858

103 87 19.44 (s, 1H), 7.96 (bs, 2H), 7.00-6.92 (m, 5H), 6.15 (bs, 2H),3.27-0.72 (m, 46H). 116.9 (s) C840

110 95 19.32 (s, 1H), 7.71 (d, 2H, J_(H—H) = 8.5 Hz), 7.37 (t, 4H,J_(H—H) = 7.5 Hz), 7.05-6.95 (m, 7H), 6.77 (t, 2H, J_(H—H) = 7.5 Hz),6.72 (s, 2H), 6.19 (s, 2H), 3.44-3.26 86.7 (s) (m, 6H), 2.68 (s, 6H),2.58- 2.55 (m, 4H). 2.28 (s, 6H), 2.17 (s, 3H), 1.85 (s, 3H). C849

95 81 19.11 (s, 1H), 7.64 (d, 2H, J_(H—H) = 5.9 Hz), 7.17 (t, 1H,J_(H—H) = 6.8 Hz), 7.11-6.97 (m, 7H), 6.84 (t, 2H, J_(H—H) = 8.8 Hz),6.80 (s, 2H), 6.16 (s, 2H), 3.43-3.23 107.9 (s) (m, 12H), 2.73-2.65 (m,11H). 2.26 (s, 6H), 2.22 (s, 3H), 2.08 (s, 3H), 1.82 (s, 3H) C850

93 80 19.65 (s, 1H), 9.30 (bs, 2H), 7.08-6.89 (m, 5H), 6.53 (bs, 2H),3.30-0.77 (m, 54H). 92.1 (s) C825

101 89 19.55 (d, 1H, J_(H—H) = 11.2 Hz), 8.19 (bs, 2H), 7.16-6.94 (m,3H), 6.85 (s, 2H), 6.16 (bs, 2H), 4.18- 4.11 (m, 1H), 3.42-3.25 (m, 4H),2.76 (s, 6H), 2.36 (s, 145.9 (s) 6H), 2.17 (s, 3H), 1.80 (s, 3H),1.69-1.03 (m, 18H), 0.94 (d, 6H, J_(H—H) = 5.9 Hz) C832

96 84 19.74 (d, 1H, J_(H—H) = 11.2 Hz), 8.17 (bs, 2H), 7.10-6.88 (m,5H), 6.65- 6.63 (m, 2H), 6.16 (bs, 2H), 6.11 (s, 2H), 3.44-3.26 (m, 4H),2.75 (s, 6H), 2.36 (s, 92.0 (s) 6H), 2.19 (s, 3H), 1.80 (s, 3H),1.58-0.93 (m, 22H). C865

89 75 19.53 (s, 1H), 8.24 (bs, 2H), 7.18-6.89 (m, 5H), 6.17 (bs, 2H),4.06-4.01 (m, 1H), 3.43- 3.26 (m, 4H), 2.77 (s, 6H), 2.37 (s, 6H), 2.21(s, 3H), 1.82 (s, 3H), 150.3 (s) 1.78-1.01 (m, 32H). C850n

82 54 (400 MHz; C₆D₆): δ 19.47 (s, 1H), 8.46 (bs, 1H), 7.14 (m, 1H),7.01 (t, J = 7.7 Hz, 2H), 6.94 (s, 3H), 6.20 (m, 2H), 3.44- 3.17 (m,4H), 3.04-2.75 (161.8 MHz; C₆D₆): δ 133.0 (s) (m, 11H), 2.75- 2.56 (s,6H), 2.22 (s, 3H), 1.82 (s, 3H), 1.69-1.50 (m, 5H), 1.41 (s, 11H), 1.28(s, 7H), 1.08- 0.75 (m, 3H). C851

92 78 (400 MHz; C₆D₆): δ 19.70 (s, 1H), 8.30 (bs, 2H), 7.19 (m, 1H),7.04- 6.98 (m, 2H), 6.93 (s, 2H), 6.25 (s, 2H), 3.43- 3.16 (m, 4H), 2.86(s, 6H), (161.8 MHz; C₆D₆): δ 118.7 (s) 2.85-2.77 (m, 12H), 2.48 (s,6H), 2.22 (s, 3H), 1.82 (s, 3H), 1.48- 1.34 (m, 6H), 1.29 (m, 12H)

Catalytic Activity of Complexes Example 27 RCM of DiethylDiallylmalonate

Ring closing metathesis reactions of diethyl diallylmalonate were run inthe presence of different catalysts of the invention. In an argon filledglovebox, diethyl diallylmalonate (0.200 mL, 0.827 mmol), catalyst(0.021 mmol) and toluene (4 mL) were combined in a 40 mL scintillationvial equipped with a magnetic stir bar. The resulting reaction wasstirred at 80° C. and analyzed by gas chromatography.

entry catalyst time % yield  1 C609 1 15  2 3 30  3 5 36  4 20 50  5C600 1 1  6 3 1  7 5 1  8 20 1  9 C591 1 3 10 3 5 11 5 6 12 20 9

Example 28 Vinyl Ether Quenching Experiments

The catalysts of the invention show fast initiation, as indicated by thevinyl ether quenching experiments. For example, the initiation rate ofthe C832 complex is about two orders of magnitude faster than the C849analogue.

FIG. 10 shows the vinyl ether quenching experiments for catalysts: C849,C865, C825, C850, C852, and C832. FIG. 11 shows the vinyl etherquenching experiments for catalysts: C831, C840, C849, and C858. FIG. 12shows the vinyl ether quenching experiments for catalysts: C848, C852,C855, and C858.

Example 29 ROMP Reactions

The catalytic activity of the complexes according to the invention, wasevaluated in ROMP reactions as follows. A 250 mL beaker was filled with100 g of DCPD-HT monomer and 50 ppm of CHP (cumene hydroperoxide). Themonomer was equilibrated to the desired temperature in an oil bath (30°C.+/−0.5° C.). A J-Type thermocouple was suspended directly into thecenter of the monomer. The catalyst under study was dissolved in solvent(either toluene or CH₂Cl₂) to form a catalyst solution and the catalystsolution was then added to the monomer at a molar ratio of 45,000:1(monomer:catalyst) to form a ROMP composition. Addition of the catalystto the monomer to form the ROMP composition denoted the start of theROMP reaction and hence, this was time point zero. Temperature readingswere recorded using the thermocouple. The exotherm time was determinedby measuring the amount of time that passed (i.e., the time difference)between time point zero and the time point that a propagating interfaceof the ROMP composition was first visually observed as the ROMPcomposition transitioned from a liquid state or gel state to a curedpolymer state. ROMP reactions were stopped 2 hours after addition of thecatalyst solution to the monomer. Time to exotherm is expressed by:slow >120 minutes; moderate 30-120 minutes; medium 1-<30 minutes; fast<1 minute and peak exotherm temperature are shown in Table 7.

TABLE 7 DCPD-HT Monomer Time to Exotherm Peak Exotherm CatalystTemperature (° C.) (min.) Temperature (° C.)

30 medium 192

30 moderate 192

30 moderate 192

30 moderate 188

30 slow 186

What is claimed is:
 1. An olefin metathesis catalyst represented byFormula (I):

wherein: M is ruthenium or osmium; X¹ and X² are independently halogen,trifluoroacetate, per-fluorophenols or nitrate; L¹ is a ligandrepresented by the structure of Formula (II), or is a N-HeterocyclicCarbene ligand represented by the structure of Formula (III):

R¹ is unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂; R² is unsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄aryl), unsubstituted saturated N-heterocycle, substituted saturatedN-heterocycle, —NH(C₁-C₂₄ alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl),—N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆alkylene)(C₅-C₂₄ aryl)]₂; R³ is unsubstituted (C₅-C₂₄ aryl), substituted(C₅-C₂₄ aryl), unsubstituted saturated N-heterocycle, or substitutedsaturated N-heterocycle; Y is CR⁴ or N; R⁴ is hydrogen, unsubstituted(C₁-C₁₂ alkyl), or substituted (C₁-C₁₂ alkyl); R⁵ and R⁶ areindependently hydrogen, unsubstituted (C₅-C₂₄ aryl), or substituted(C₅-C₂₄ aryl); Q is a two-atom linkage represented by structures—[CR⁷R⁸]_(s)—[CR⁹R¹⁰]_(t)— or —[CR¹¹═CR¹²]—; R⁷, R⁸, R⁹ and R¹⁰ areindependently hydrogen, unsubstituted (C₁-C₂₄ alkyl), substituted(C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), or substituted (C₅-C₂₄aryl); R¹¹ and R¹² are independently hydrogen, unsubstituted (C₁-C₂₄alkyl), substituted (C₁-C₂₄ alkyl), unsubstituted (C₅-C₂₄ aryl), orsubstituted (C₅-C₂₄ aryl); and “s” and “t” are independently 1 or
 2. 2.The olefin metathesis catalyst according to claim 1, represented by thestructure of Formula (VI):

wherein: X¹ is Cl; X² is Cl; R¹ is morpholino, thiomorpholino,1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; R² is phenyl, morpholino, thiomorpholino,1-methyl-piperazino, piperidino, N-acetyl piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; and R³ is phenyl or morpholino.
 3. The olefinmetathesis catalyst according to claim 2, selected from:


4. The olefin metathesis catalyst according to claim 1, represented bythe structure of Formula (VII):


5. The olefin metathesis catalyst according to claim 4, represented bythe structure of Formula (VIII):

wherein: X¹ is Cl; X² is Cl; R¹ is morpholino, thiomorpholino,1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; R² is phenyl, morpholino, thiomorpholino,1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino,N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, ordi-iso-propylamino; R³ is phenyl or morpholino; and R⁵ and R⁶ areindependently 2,4,6-trimethyl-phenyl, 2,6-di-iso-propylphenyl,2-iso-propylphenyl or 2-methyl-6-iso-propylphenyl; Q is a two-atomlinkage represented by structure —[CR⁷R⁸]_(s)—[CR⁹R¹⁰]_(t)—; R⁷, R⁸, R⁹and R¹⁰ are independently hydrogen; and “s” and “t” are independently 1.6. The olefin metathesis catalyst according to claim 5, selected from:


7. A method of synthesizing an olefin metathesis catalyst represented bythe structure of Formula (A):

the method comprising contacting an olefin metathesis catalystrepresented by the structure of Formula (VIII):

with a PR^(d)R^(e)OR^(f) ligand at room temperature in an inert solvent,wherein: X¹ and X² are independently halogen, trifluoroacetate,per-fluorophenols or nitrate; R¹ is unsubstituted saturatedN-heterocycle, substituted saturated N-heterocycle, —NH(C₁-C₂₄ alkyl),—N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl), —N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂; R² isunsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl), unsubstitutedsaturated N-heterocycle, substituted saturated N-heterocycle, —NH(C₁-C₂₄alkyl), —N(C₁-C₂₄ alkyl)₂, —NH(C₅-C₂₄ aryl), —N(C₅-C₂₄ aryl)₂, —N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl) or —N[(C₁-C₆ alkylene)(C₅-C₂₄ aryl)]₂; R³ isunsubstituted (C₅-C₂₄ aryl), substituted (C₅-C₂₄ aryl), unsubstitutedsaturated N-heterocycle or substituted saturated N-heterocycle; R⁵ andR⁶ are independently hydrogen, unsubstituted C₅-C₂₄ aryl, or substitutedC₅-C₂₄ aryl; generally R⁵ and R⁶ are independently substituted C₅-C₂₄aryl with one to three unsubstituted (C₁-C₆ alkyl) groups or substituted(C₁-C₆ alkyl) groups; R^(d) is unsubstituted C₁-C₁₀ alkyl, substitutedC₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl,substituted C₃-C₈ cycloalkyl or unsubstituted C₃-C₈ cycloalkyl; R^(e) isunsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl orunsubstituted C₃-C₈ cycloalkyl; and R^(f) is unsubstituted C₁-C₁₀ alkyl,substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀aryl, substituted C₃-C₈ cycloalkyl or unsubstituted C₃-C₈ cycloalkyl. 8.The method according to claim 7, wherein: X¹ is Cl; X² is Cl; R¹ ismorpholino, thiomorpholino, 1-methyl-piperazino, piperidino,N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino,diethylamino, methyl-phenylamino, or di-iso-propylamino; R² is phenyl,morpholino, thiomorpholino, 1-methyl-piperazino, piperidino,N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino,diethylamino, methyl-phenylamino, or di-iso-propylamino; and R³ isphenyl or morpholino R⁵ is 2,4,6-trimethylphenyl; R⁶ is2,4,6-trimethylphenyl; R^(d) is phenyl; R^(e) is phenyl; and R^(f) isphenyl, methyl, p-(OMe)phenyl, or iso-propyl.